Fungal laccases catalyse the oxidative transformation of hydroxylated phenylureas

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Fungal laccases catalyse the oxidative transformation of

hydroxylated phenylureas

Claude Jolivalt, Luc Neuville, Francois-Didier Boyer, Lucien Kerhoas,

Christian Mougin

To cite this version:

Claude Jolivalt, Luc Neuville, Francois-Didier Boyer, Lucien Kerhoas, Christian Mougin. Fungal

laccases catalyse the oxidative transformation of hydroxylated phenylureas. SETAC Europe 16th

Annual Meeting, May 2006, La Haye, Netherlands. 2006. �hal-01605389�

1

Identification and formation pathway of laccase-mediated oxidation products formed from hydroxy-phenylureas

UR Phytopharmacie et Médiateurs Chimiques,

*New address: UR Physicochimie et Ecotoxicologie des Sols d’Agrosystèmes Contaminés

INRA, Versailles, France.

Institut National de la Recherche Agronomique

UMR Synthèse Sélective Organique et Produits Naturels, CNRS / ENSCP, Paris, France.

Claude JOLIVALT, Luc NEUVILLE, François-Didier BOYER, Lucien KERHOAS, Christian MOUGIN*

Results

Structure of laccase : Bertrand et al., Biochemistry (2002) 41, 7325- 7333. Applications: Mougin et al., Environ. Chem. Lett. (2003) 1, 145-148. Production: Jolivalt et al., App. Microbiol. Biotechnol. (2005) 66, 450-456. Contacts: Dr Claude Jolivalt (Claude-Jolivalt@enscp.fr)

Dr Christian Mougin (mougin@versailles.inra.fr) Laccasesare blue multicopper oxidases that catalyze the oxidation of a large range of phenols and arylamines. These enzymes are released in the environment.

Bertrand et al. (2002) Laccase from the white rot fungus T. versicolor

The pH of the reaction has a strong influence on both the kinetics of the reaction and the nature of the transformation products, whose structures have been characterized. Hydroxylation is one of the functionalization route for phenylureas in environmental degradation conditions. Phenylureas and their hydroxylated metabolites

►Are fungal laccases involved in the transformation of hydroxy-phenylureas?

Phenylureasare mainly used asherbicides for the selective protection of cereal crops and for the maintenance of roads and railways. Others enter the industrial processes as biocides and/or protective agents against oxidation.

Their degradation in the environment is governed by abiotic (pH, température, light) and the presence of micro-organisms such as bacteria and fungi.

HNN O Cl Diuron Cl Photolyse HNN O OH Cl 4HF-3Cl HNN O Cl Monuron HNN O OH 4HF Plants

These results demonstrate that fungal laccases exhibit a great potential to assist the transformation of hydroxy-phenylureas.

Conclusion

The quinones further react with remaining substrate in solution to give hetero-oligomers via carbon-carbon or carbon-oxygen bond formation.

Cu1 Cu3a Cu3b Cu2 (T1) (T2/T3) O2 e-2 He-2O Reducing substrate (phenol, arylamine)

Quinones are formed as final transformation products. At pH 3 and 5 OH R NH O Me2N O R NH O Me2N O R NH O Me2N -1 e lacc O R N O Me2NH O R NH O Me2N O H H O R O O R NH O Me2N O H - H H2O O R N O Me2N - HpH=5 pH=3 - H -1 e lacc - Me2NCONH2 I: R = H II: R = Cl III: R = H V: R = Cl 4HF: R = H 4HF-3Cl: R = Cl At pH 5-6 O HHNO NMe2 OHNO NMe2 OH NO NMe2 O N H O NMe2H -1 e lacc Radical dimerisation Tautomerisation OHH N Cl O NMe2 O H N H Cl O NMe2 Cl Cl Cl Cl OHHN O NMe2 Cl OHNO NMe2 Cl 2HF-4Cl VII -1 e lacc OHH NO NM e2 OH NH O NMe2 OH N O O NMe2 OHHN O NMe2 2 OH N O NH O NMe2 O NMe2 NMe2 and NHO -2 e lacc -2 H -2 e lacc -2 H VI VIbis 2HF - H - H